Polymerization of olefins

ABSTRACT

Olefins are polymerized by novel transition metal complexes of selected iminocarboxylate and iminoamido ligands, sometimes in the presence of cocatalysts such as alkylaluminum compounds or neutral Lewis acids. Olefins which may be (co)polymerized include ethylene, α-olefins, and olefins containing polar groups such as olefinic esters for example acrylate esters. Also described are certain “Zwitterionic” transition metal complexes as polymerization catalysts for making polar copolymers. The resulting polymers are useful as thermoplastics and elastomers.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority under 35 U.S.C. §119 from U.S.Provisional Application Ser. Nos. 60/208,087 (filed May 31, 2000),60/211,601 (filed Jun. 15, 2000) and 60/214,036 (filed Jun. 23, 2000),all of which are incorporated by reference herein as if fully set forth.

FIELD OF THE INVENTION

Selected transition metal complexes of iminocarboxylate and iminoamidoligands, sometimes in the presence of certain cocatalysts, are catalystsfor the (co)polymerization of olefins such as ethylene, α-olefins, andcertain polar olefins such as olefinic esters. Preferred transitionmetals include nickel, titanium and zirconium. Also described arecertain “Zwitterionic” transition metal complexes as polymerizationcatalysts for making polar copolymers.

TECHNICAL BACKGROUND

Olefins may be polymerized by a variety of transition metal containingcatalysts, for example metallocene and Ziegler-Natta type catalysts.More recently, late transition metal containing polymerization catalystshave also been discovered, and among them are nickel and othertransition metal containing catalysts in which the metal atom iscomplexed to a monoanionic and presumed bidentate ligand, see forinstance WO9842664, WO9842665, U.S. Pat. Nos. 6,060,569, 6,174,975 andS. D. Ittel, et al., Chem. Rev., vol. 100, p. 1169-1203 (2000) (andreferences cited therein). S. Y. Desjardins, et al., J. Organometal.Chem., vol. 515, p. 233-243 (1996), ibid., vol. 544, p. 163-174 (1997),describe the oligomerization/polymerization of ethylene using nickelcomplexes of certain pyridine carboxylates.

U.S. Pat. No. 6,174,976 describes the use of certain neutral nickelcomplexes of ligands containing imino and carboxylate groups topolymerize hydrocarbon monoolefins.

In the following references, Zwitterionic nickel catalysts based onphosphine carboxylate ligands were utilized to carry out ethyleneoligomerizations; however, polar monomers were not incorporated in anyof the oligomers made with these systems: Komon, Z. J. A., et. al., J.Am. Chem. Soc., 122, 1830-1831 (2000); Komon, Z. J. A., et. al., J. Am.Chem. Soc., 122, 12379-12380 (2000).

Zwitterionic systems have been proposed in U.S. Pat. Nos. 6,103,658 and6,200,925, but no polar monomers were incorporated in any of thepolymers made with these systems.

All of the above publications are incorporated by reference herein forall purposes as if fully set forth.

None of these publications describes the complexes disclosed herein.Since polyolefins are important commercial materials, new catalysts fortheir manufacture are constantly being sought.

SUMMARY OF THE INVENTION

This invention concerns a process for the polymerization of olefins,comprising the step of contacting, under olefin polymerizing conditions,a monomer component comprising one or more of an olefin of the formulaH₂C=CHR⁴, a norbornene, a styrene, a cyclopentene or a polar olefin,especially an olefin of the formula H₂C=CHR⁴ or a polar olefin of theformula H₂C=CHR⁵CO₂R⁶, with a transition metal complex of a ligand ofthe formula

wherein:

Y is oxo, NR¹² or PR¹²

z is O, NR¹³, S or PR¹³;

each of R¹, R² and R³ is independently hydrogen, hydrocarbyl,substituted hydrocarbyl or a functional group;

n is 0 or 1;

R⁴ is hydrogen, alkyl or substituted alkyl;

R⁵ is a covalent bond, alkylene or substituted alkylene;

R⁶ is hydrogen, a metal cation, hydrocarbyl or substituted hydrocarbyl;

each R¹² is independently hydrogen, hydrocarbyl, substituted hydrocarbylor a functional group;

each R¹³ is independently hydrogen, hydrocarbyl, substituted hydrocarbylor a functional group;

and provided that any two of R¹, R² and R³ geminal or vicinal to oneanother taken together may form a ring.

In the above mentioned process, the transition metal complex of (I) mayin and of itself be an active catalyst, or may be “activated” by contactwith a cocatalyst/activator as further described below.

The present invention also concerns the ligand of the formula (I),transition metal complexes thereof, and polymerization catalystcomponents comprising these transition metal complexes.

This invention also concerns a process for the manufacture of a polarcopolymer, wherein one or more hydrocarbon olefins, one or more polarolefins, and a polymerization catalyst system having a transition metalcomplex component containing a transition metal of groups 6-11 or alanthanide metal, are contacted under polymerizing conditions to formsaid polar copolymer, wherein the transition metal complex componentcomprises a Zwitterionic complex.

These and other features and advantages of the present invention will bemore readily understood by those of ordinary skill in the art from areading of the following detailed description. It is to be appreciatedthat certain features of the invention which are, for clarity, describedbelow in the context of separate embodiments, may also be provided incombination in a single embodiment. Conversely, various features of theinvention which are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any subcombination.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Herein, certain terms are used. Some of them are:

A “hydrocarbyl group” is a univalent group containing only carbon andhydrogen. As examples of hydrocarbyls may be mentioned unsubstitutedalkyls, cycloalkyls and aryls. If not otherwise stated, it is preferredthat hydrocarbyl groups (and alkyl groups) herein contain 1 to about 30carbon atoms.

By “substituted hydrocarbyl” herein is meant a hydrocarbyl group thatcontains one or more substituent groups which are inert under theprocess conditions to which the compound containing these groups issubjected (e.g., an inert functional group, see below). The substituentgroups also do not substantially detrimentally interfere with thepolymerization process or operation of the polymerization catalystsystem. If not otherwise stated, it is preferred that substitutedhydrocarbyl groups herein contain 1 to about 30 carbon atoms. Includedin the meaning of “substituted” are chains or rings containing one ormore heteroatoms, such as nitrogen, oxygen and/or sulfur, and the freevalence of the substituted hydrocarbyl may be to the heteroatom. In asubstituted hydrocarbyl, all of the hydrogens may be substituted, as intrifluoromethyl.

By “(inert) functional group” herein is meant a group, other thanhydrocarbyl or substituted hydrocarbyl, which is inert under the processconditions to which the compound containing the group is subjected. Thefunctional groups also do not substantially deleteriously interfere withany process described herein that the compound in which they are presentmay take part in. Examples of functional groups include, for example,halo (fluoro, chloro, bromo and iodo), ether such as —OR²² wherein R²²is hydrocarbyl or substituted hydrocarbyl, silyl, substituted silyl,thioether and tertiary amino. In cases in which the functional group maybe near a transition metal atom, the functional group alone should notcoordinate to the metal atom more strongly than the groups in thosecompounds that are shown as coordinating to the metal atom, that is theyshould not displace the desired coordinating group.

By a “cocatalyst” or a “catalyst activator” is meant one or morecompounds that react with a transition metal compound to form anactivated catalyst species. One such catalyst activator is an “alkylaluminum compound” which, herein, is meant a compound in which at leastone alkyl group is bound to an aluminum atom. Other groups such as, forexample, alkoxide, hydride and halogen may also be bound to aluminumatoms in the compound.

By “neutral Lewis base” is meant a compound, that is not an ion, whichcan act as a Lewis base. Examples of such compounds include ethers,amines, thioethers, olefins and organic nitrites.

By “neutral Lewis acid” is meant a compound, that is not an ion, whichcan act as a Lewis acid. Examples of such compounds include boranes,alkylaluminum compounds, aluminum halides and antimony [V] halides.

By “cationic Lewis acid” is meant a cation which can act as a Lewisacid. Examples of such cations are sodium and silver cations.

By an “empty coordination site” is meant a potential coordination siteon a transition metal atom that does not have a ligand bound to it. Thusif an olefin molecule (such as ethylene) is in the proximity of theempty coordination site, the olefin molecule may coordinate to the metalatom.

By a “ligand into which an olefin molecule may insert between the ligandand a metal atom”, or a “ligand that may add to an olefin”, is meant aligand coordinated to a metal atom which forms a bond (L-M) into whichan olefin molecule (or a coordinated olefin molecule) may insert tostart or continue a polymerization. For instance, with ethylene this maytake the form of the reaction (wherein L is a ligand):

By a “ligand which may be displaced by an olefin” is meant a ligandcoordinated to a transition metal which, when exposed to the olefin(such as ethylene), is displaced as the ligand by the olefin.

By a “monoanionic ligand” is meant a ligand with one negative charge.

By a “neutral ligand” is meant a ligand that is not charged.

“Alkyl group” and “substituted alkyl group” have their usual meaning(see above for substituted under substituted hydrocarbyl). Unlessotherwise stated, alkyl groups and substituted alkyl groups preferablyhave 1 to about 30 carbon atoms.

By “aryl” is meant a monovalent aromatic group in which the free valenceis to the carbon atom of an aromatic ring. An aryl may have one or morearomatic rings which may be fused, connected by single bonds or othergroups.

By “substituted aryl” is meant a monovalent aromatic group substitutedas set forth in the above definition of “substituted hydrocarbyl”.Similar to an aryl, a substituted aryl may have one or more aromaticrings which may be fused, connected by single bonds or other groups;however, when the substituted aryl has a heteroaromatic ring, the freevalence in the substituted aryl group can be to a heteroatom (such asnitrogen) of the heteroaromatic ring instead of a carbon.

By a “π-allyl group” is meant a monoanionic ligand comprised of 1 sp³and two sp² carbon atoms bound to a metal center in a delocalized η³fashion indicated by

The three carbon atoms may be substituted with other hydrocarbyl groupsor functional groups.

By a “styrene” herein is meant a compound of the formula

wherein R⁴³, R⁴⁴, R⁴⁵, R⁴⁶ and R⁴⁷ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group, all of whichare inert in the polymerization process. It is preferred that all ofR⁴³, R⁴⁴, R⁴⁵, R⁴⁶ and R⁴⁷ are hydrogen. Styrene (itself) is a preferredstyrene.

By a “norbornene” is meant ethylidene norbornene, dicyclopentadiene or acompound of the formula

wherein R⁴⁰ is hydrogen or hydrocarbyl containing 1 to 20 carbon atoms.It is preferred that R⁴⁰ is hydrogen or alkyl, more preferably hydrogenor n-alkyl, and especially preferably hydrogen. The norbornene may besubstituted by one or more hydrocarbyl, substituted hydrocarbyl orfunctional groups in the R⁴⁰ or other positions, with the exception ofthe vinylic hydrogens, which remain. Norbornene (itself) is a preferrednorbornene.

By a “cyclopentene” herein is meant cyclopentene or a substitutedcyclopentene. Preferred cyclopentenes are cyclopentene, 1- or3-methylcyclopentene and 1- or 3-ethylcyclo-pentene, andcyclopentylcyclopentene, and cyclopentene is more preferred.

By “E_(s)” is meant a parameter to quantify steric effects of variousgroupings, see R. W. Taft, Jr., J. Am. Chem. Soc., vol. 74, p. 3120-3128(1952), and M. S. Newman, Steric Effects in Organic Chemistry, JohnWiley & Sons, New York, 1956, p. 598-603, which are both hereby includedby reference. For the purposes herein, the E_(s) values are thosedescribed for o-substituted benzoates in these publications. If thevalue of E_(s) for a particular group is not known, it can be determinedby methods described in these references.

By “aryl substituted in at least one position vicinal to the free bondof the aryl group,” is meant the bond to one of the carbon atoms next tothe free valence of the aryl group is something other than hydrogen. Forexample for a phenyl group, it would mean the 2 position of the phenylgroup would have something other than hydrogen attached to it. A1-naphthyl group already has something other than hydrogen attached toone of the vicinal carbon atoms at the fused ring junction, while a2-napthyl group would have to be substituted in either the 1 or 3positions to meet this limitation. A preferred aryl substituted in atleast one position vicinal to the free bond of the aryl group is aphenyl group substituted in the 2 and 6 positions, and optionally in theother positions.

By a “polar (co)monomer” or “polar olefin” is meant an olefin whichcontains elements other than carbon and hydrogen. When copolymerizedinto a polymer the polymer is termed a “polar copolymer”. Useful polarcomonomers are found in U.S. Pat. No. 5,866,663, WO9905189, WO9909078and WO9837110, and S. D. Ittel, et al., Chem. Rev., vol. 100, p.1169-1203(2000), all of which are incorporated by reference herein forall purposes as if fully set forth. Also included as a polar comonomeris CO (carbon monoxide).

By “under polymerization conditions” is meant the conditions for apolymerization that are usually used for the particular polymerizationcatalyst system being used. These conditions include paraneters such aspressure, temperature, catalyst and cocatalyst (if present)concentrations, the type of process such as batch, semibatch,continuous, gas phase, solution or liquid slurry etc., except asmodified by conditions specified or suggested herein. Conditionsnormally done or used with the particular polymerization catalystsystem, such as the use of hydrogen for polymer molecular weightcontrol, are also considered “under polymerization conditions”. Otherpolymerization conditions such as presence of hydrogen for molecularweight control, other polymerization catalysts, etc., are applicablewith this polymerization process and may be found in the referencescited and incorporated herein.

The polymerizations herein are carried out by a transition metal complexof anion (I). In (I), and in all complexes and compounds containing (I)or its parent conjugate acid, it is preferred that:

Y is oxo or NR¹²;

Z is O or NR¹³;

n is 0; and/or

R¹ is hydrocarbyl or hydrogen, more preferably hydrogen or alkyl;especially preferably alkyl, and particularly methyl; and/or

R² and R³, when present (n is 1), are each independently hydrocarbyl orhydrogen, more preferably hydrogen or alkyl; especially preferablymethyl or hydrogen; and/or

R¹² and R¹³ are each independently hydrocarbyl or substitutedhydrocarbyl, more preferably aryl, substituted aryl or alkyl; morepreferably 9-phenanthryl, 1- or 2-naphthyl or substituted 1- or2-naphthyl, or

wherein each of R⁷, R⁸, R⁹, R¹⁰ and R¹¹ is independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group. In anotherpreferred form, one or both of R¹² and/or R¹³ are aryl or substitutedaryl in which at least one bond vicinal to the free bond of the aromaticgroup is substituted, or R¹² and/or R¹³ are a group with an E_(s) ofless than about −1.0, more preferably less than about −1.5, or both.

In (I) and its complexes, more specific preferred combinations are:

when Y is O (oxo) and Z is NR¹³; R¹ is hydrogen or hydrocarbyl, morepreferably alkyl or aryl; R¹³ is hydrocarbyl or substituted hydrocarbylhaving an E_(s) of less than −1.0, or aryl or substituted aryl in whichat least one bond vicinal to the free bond of the aromatic group issubstituted, more preferably 2,6-disubstituted phenyl (optionally withone or more of the other positions on the phenyl group substituted); or

when Y is NR¹² and Z is NR¹³; R¹ is hydrogen or hydrocarbyl, morepreferably alkyl or aryl; one or both of R¹² and R¹³ is hydrocarbyl orsubstituted hydrocarbyl having an E_(s) of less than −1.0, or aryl orsubstituted aryl in which at least one bond vicinal to the free bond ofthe aromatic group is substituted, more preferably R¹² is2,6-disubstituted phenyl (optionally with one or more of the otherpositions on the phenyl group substituted).

In (II) it is preferred that one or both of R⁷ and R¹¹ are other thanhydrogen, more preferably hydrocarbyl or a functional group, especiallypreferably alkyl containing 1 to 6 carbon atoms, aryl (such as pehnyl ora hydrocarbyl substituted phenyl such as 4-t-butylphenyl), halo oralkoxy.

A specific preferred ligand (I) (and its corresponding conjugate acidand transition metal complexes) include one in which R¹ is methyl; n is0; Y is NR¹², R¹² is (II); R⁸, R⁹ and R¹⁰ are hydrogen; and R⁷ and R¹¹are isopropyl.

In transition metal complexes of (I), useful transition metals includeGroup 3-11 (IUPAC) transition metals and lanthanide metals such as Ni,Pd, Pt, Fe, Co, Ti, Zr, V, Hf, Cr, Mn, Ru, Rh, Re, Os, Ir, Cu and therare earths (lanthanides). Preferred transition metals are Ni, Zr, Ti,Fe, Co and Cu, and Ni, Ti and Zr are more preferred. When Ni, Fe or Coare the transition metals a preferred oxidation state is [II], when Zror Ti are the transition metals a preferred oxidation state is [IV], andwhen Cu is the transition metal preferred oxidation states are [I] and[II].

The complexes of the transition metals may contain one or two of theligands (I) per transition metal atom, depending on the particulartransition metal. For example early transition metals which may bepentacoordinate or hexacoordinate may have one or two ligands per metalatom respectively, as exemplified in the structures

wherein, for example, M (the transition metal) may be Ti [IV] or Zr[IV],and each L¹ is a monodentate, monoanionic ligand such as chloride.

For some late transition metals such as Ni which tend to betetracoordinate, a typical complex may be

wherein, for example, M (the transition metal) is Ni[II], L¹ is amonoanionic, monodentate ligand such as chloride or methyl, and L² is amonodentate neutral ligand such as acetonitrile, or an emptycoordination site, or L¹ and L² taken together are a monoanionic,bidentate ligand such as a π-allyl group.

Although the complexes of (I) are drawn with (I) as a bidentate ligandit is to be understood that this is for convenience only in representingthese complexes, and any transition metal complex of (I), whether (I) ismonodentate, bidentate, etc., is included within the meaning of acomplex of (I).

It is believed that, in the active polymerization catalyst speciesherein, at least one of the ligands (e.g., L¹) is preferably a ligandthat may add to an olefin. It is further believed that, in the latetransition metal active polymerization catalyst species herein, anotherof the ligands (e.g., L²) is a neutral ligand which may be displaced byan olefin, or an empty coordination site, or the olefin itself. Examplesof ligands that may add to an olefin include hydrocarbyl and substitutedhydrocarbyl (especially phenyl and alkyl, and particularly methyl),hydride and acyl. Examples of ligands which may be displaced by ethyleneinclude phosphines (such as triphenylphosphine), nitrites (such asacetonitrile), ethers (such as ethyl ether), pyridine and tertiaryalkylamines (such as TMEDA (N,N,N′,N′-tetramethylethyenediamine)).

Herein, as indicated above, ligands that may add to an olefin can be L¹,and ligands which may be displaced by ethylene may be L², as forinstance shown in (V) and (VI).

Particularly at the beginning of the polymerization, L¹ and L² takentogether may be a bidentate monoanionic ligand into which an olefinmolecule (such as ethylene) may insert between that ligand and thetransition metal atom, such as π-allyl- or π-benzyl-type ligands such as

wherein R is hydrocarbyl. In this instance, sometimes it may benecessary to add a neutral Lewis acid cocatalyst such as triphenylboraneor tris(pentafluorophenyl)borane to initiate the polymerization, seebelow and for instance U.S. Pat. No. 5,880,241, which is incorporated byreference herein for all purposes as if fully set forth. For a summaryof which ligands olefins may insert into (between the ligand andtransition metal atom) see for instance J. P. Collman, et al.,Principles and Applications of Organotransition Metal Chemistry,University Science Books, Mill Valley, Calif., 1987.

If for instance L¹ is not a ligand into which ethylene may insertbetween it and the transition metal atom, it may be possible to add acocatalyst that may convert L¹ into a ligand which will undergo such aninsertion. Thus if L¹ is halo such as chloride or bromide, carboxylateor acetylacetonate, it may be converted to hydrocarbyl such as alkyl byuse of a suitable alkylating agent such as an alkylaluminum compound, aGrignard reagent or an alkyllithium compound. It may be converted tohydride by used of a compound such as sodium borohydride.

It is preferred that the alkylating compound (cocatalyst or activator)be both an alkylating compound and a neutral Lewis acid. A preferredcocatalyst is an alkylaluminum compound, and useful alkylaluminumcompounds include trialkylaluminum compounds such as triethylaluminum,trimethylaluminum and tri-i-butylaluminum, alkyl aluminum halides suchas diethylaluminum chloride and ethylaluminum dichloride, andaluminoxanes such as methylaluminoxane. Alternatively, a combination ofan alkylating agent (which may be a relatively weak Lewis acid) andanother stronger neutral Lewis acid may be present as the cocatalyst(s).Even if L¹ is already a ligand into which ethylene may insert, it may beadvantageous to have a neutral Lewis acid present as a cocatalyst. It ispreferred when a late transition metal, especially Ni, is used, that aneutral Lewis acid be present, especially at lower process temperatures.

Once the polymerization has started on a particular transition metalsite, the ligand into which an olefin may insert will often be a ligandwhich is in fact the growing polymer chain whose composition will be themonomer(s) being polymerized and the end group the original L¹ which thefirst olefin molecule inserted into (between the ligand and metal). Thispolymer ligand may be represented by the group −PL¹, wherein P is adivalent “polymeric” (but which may have only one or few repeat units attimes), and will be understood to contain one or more repeat unitsderived from the monomer(s) used. If chain transfer occurs, for instanceby β-hydride elimination to form a hydride ligand on the transitionmetal, the end group of the next polymer chain will be hydrogen.

A general formula for a transition metal complex useful herein can bewritten as (L¹)_(x)(L²)_(y)(L³)_(z)M (VIII) wherein L¹ and L² are asdefined above, L³ is (I), z is 1 or 2, M is a transition metal ofoxidation state q, y is an integer of 1 to 3, and x=(q−z). L¹ and L² mayhave the variations mentioned above, and when L¹ and L² are theindicated groups, the transition metal compound may inherently be anactive polymerization catalyst. Table 1 gives preferred transition metalcompounds (VIII). Preferred ligands L³ for these compounds are asdescribed above.

TABLE 1 M q L¹ x L² y z Ni 2 π-allyl^(a) 1^(a) π-allyl^(a) 1^(a) 1 Zr 4Cl 2 — 0 2 Zr 4 Cl 3 — 0 1 Ti 4 Cl 2 — 0 2 Ti 4 Cl 3 — 0 1 ^(a)L¹ and L²combined in a single π-allyl-type group.

Included within the meaning of the transition metal complexes of (I)herein are Lewis acid adducts of such complexes. By this is meant anadduct formed between the transition metal complex of (I) and a neutralLewis acid. The structures of such adduct complexes may often be writtenas

wherein R¹, R², R³, n, Z, Y, M, L¹ and L² are as defined above, and LA(by itself) is a neutral Lewis acid. Preferably the metal is a latetransition metal of Groups 6-11, more preferably Groups 8-11. Suitableneutral Lewis acids include boranes such astris(pentafluorophenyl)borane, triphenylborane, and aluminanes such astrihydrocarbylaluminum, especially trialkylaluminum (for exampletriethylaluminum), and others which can coordinate with the transitionmetal complex.

More generally (with other suitable ligands as well, see below) suchcomplexes, called herein Zwitterionic complexes, are particularly usefulin the copolymerization of a hydrocarbon olefin (such as ethylene) and apolar comonomer, especially vinyl polar comonomers (in a vinyl polarcomonomer the polar group is attached directly to a vinylic carbon atom,as in acrylic monomers), particularly when using a complex of a latetransition metal of Groups 8-11. Preferred metals are Pd and Ni, and Niis especially preferred. Suitable neutral Lewis acids includetris(pentafluorophenyl)borane, triphenylborane, trihydrocarbylaluminum,especially trialkylaluminum (for example triethylaluminum), and otherswhich can coordinate with the transition metal complex. Preferably theLewis acid should not react with any other component of thepolymerization catalyst system, for example not contain “active” halogengroups which may react with an alkylaluminum compound, if analkylaluminum compound is present in the polymerization process. TheLewis acid is coordinated to a Lewis base which is present in the ligandof the metal complex. Therefore, the Lewis acid may be removed fromligand (metal complex) by addition of a Lewis base which is a strongerLewis base than the group on the ligand to which the Lewis acid iscoordinated (bound). Lewis acid in this instance does not mean a Lewisacid which is relatively permanently covalently bound to the ligands,for example —B(aryl)₂ where the boron is covalently bound to a carbonatom of the ligand.

When using Zwitterionic materials to form polar comonomers, preferredhydrocarbon olefins are ethylene and H₂C=CHR⁴, wherein R⁴ is alkyl orsubstituted alkyl, preferably n-alkylene, and ethylene is especiallypreferred. A preferred polar olefin is H₂C=CHR⁵CO₂R⁶, particularlywherein R⁵ is a covalent bond, and R⁶ is hydrocarbyl or substitutedhydrocarbyl.

When the transition metal complex in the Zwitterionic compound is a Nicomplex, it is preferred that the Ni atom be coordinated to a neutralbidentate ligand or a monoanionic bidentate ligand. In order to form aZwitterionic compound using a complex of any transition metal with anyligand, the ligand will normally contain a group which is a Lewis base.The combination of this Lewis base group and neutral Lewis acid chosenwill normally have a large enough difference in Lewis acidity andbasicity to form a complex. For example a group which is a weak Lewisbase may form a Zwitterionic compound with a strong Lewis acid, and viceversa.

Generally speaking a Zwitterionic complex will be detectable using anynumber of methods. For instance it may be isolable as the Zwitterioniccomplex, and the structure proven by various methods such as X-raydiffraction or various spectroscopic methods such as NMR or infraredspectroscopy. Its presence may also be shown in solution, such as byultraviolet, infrared or NMR spectroscopy. If any of these or othermethods shows the presence of the Zwitterionic compound, it is deemedthis complex is an active polymerization catalyst.

In any of the polymerization processes herein in which a polar comonomeris copolymerized, and in any formation of any polar copolymer, it ispreferred that the molar ratio of the total of the polar comonomerspresent to any added Lewis acid is at least 2:1, preferably at least10:1. Polar comonomers, such acrylic-type monomers, have beencopolymerized in certain situations by destroying their Lewis basic (orcoordinating) character by reacting them with a Lewis acid, to form aLewis acid “salt” of the polar comonomer. While this may often help toform the polar copolymer, later removal of the stoichiometric amount(relative to the polar comonomer) of Lewis acid is difficult andexpensive.

It is also noted that when Zwitterionic complexes are used as part ofthe olefin polymerization catalyst system, even in the polymerization ofhydrocarbon olefins (no polar olefins present), such as ethylene, thereis an improvement in the polymerization, such as improved polymerproductivity and/or longer catalyst life.

In one preferred form of the present Zwitterionic compounds, the Lewisacid which complexes to the ligand in the transition metal complexpreferably is not in a position to readily interact with any polargroups on the polar copolymer which is forming, particularly polargroups very close to the metal atom on the polymerizing polymer chain.This is particularly preferred with Ni complexes.

Dreiding Stereomodels (Manufactured by Büchi Laboratory-Techniques,Ltd., Switzerland, and available in the USA from Aldrich ChemicalCompany or other sources. The Normal Set, Aldrich Catalog NumberZ24,787-1 and the Porphyrin Set, Aldrich Catalog Number Z25,644-7,together provide the parts required for this purpose) are a useful toolto understand the geometries of various catalytic complexes. Theyprovide very precise bond distances and angles while maintaining all ofthe flexibility normally associated with atom-atom bonds. They areavailable with the nickel, carbon, nitrogen, oxygen, phosphorus, sulfurand all other atoms necessary for building all of the ligands andcomplexes discussed in this case. They also come with a convenient rulerto measure distance between atom centers in Ångstroms. They are usefulto determine the potential for interaction between the polarfunctionality on the growing polymer chain and any Lewis acidic site inthe complex. Through rotation about the Ni—C bond and any other C—Cbonds in the polymer chain bound to the nickel center, the polarfunctionality is able to sweep out a conical volume of space. If thereis any available Lewis acidic site within that space (which may alsorotate into that space), it is presumed that there can be a bondinginteraction with that Lewis acidic site which would compete in anequilibrium with the nickel center for the lone pair electrons on thepolar functionality. The potential for interaction may be determinedthrough the following construct.

Starting with a square planar nickel atom, the complex is constructed bybinding the ligand to two of the adjacent coordination sites on nickel.A carbon atom is placed at a third site on nickel. The fourthcoordination site on nickel is occupied by X, and A represents a ligandor a vacant coordination site.

A solid cone is defined by the angle, θ, and the distance (in Å), λ, inthe manner shown, with the axis of the cone along the nickel-carbonbond. The maximum value possible for θ is 180°.

The conical volume of space through which the polar functionalityattached to the growing polymer chain may sweep by means of rotation ofthe Ni—C and C—C bonds is determined through use of the models. Thiscone is the Lewis Acid Interaction Cone or LAIC. The angle increases foreach additional carbon atom located between the nickel center and thepolar functionality. For instance, in the case of methyl acrylate, θvaries from 65 to 120° in going from one to three carbon atoms betweenthe nickel center and the carbonyl functionality.

These are taken herein as typical values of the LAIC for a variety ofcommercially important polar olefins. Any catalyst complex having aLewis acidic atom whose atomic center is within the LAIC may bond to theelectron pair available on the polar functionality through said Lewisacid. On the other hand, the Lewis acid in

is well outside the LAIC even at θ=130° (and is preferred herein) andwill not be involved in binding to the Lewis-basic electron pair of thepolar functionality. To be one type of preferred Lewis acid herein, theLAIC should be greater than 130°, preferably greater than about 150°.

The volume swept out by the rotating carbonyl is also limited in itsdistance, λ, from the nickel center. It may not come closer to nickelthan the bonding distance of just over 2 Å. Maximizing the distance fromthe metal center, one observes 4.5, 5.0 and 6.5 Å, respectively for one,two and three carbons between nickel and the carbonyl group. Thesedistances impose a further constraint upon the position of the Lewisacid, but the distance from the metal center is seldom a limitation inthe construction of ligands.

When Z in (I) is O, the ligand may be made by reaction of an amineR¹²NH₂ with a metal salt, preferably an alkali metal salt, of anappropriate carboxylic acid

wherein R¹, R², R³, R¹² and n are as defined above. This reaction yieldsthe ligand (I) as its (alkali) metal salt. This salt may then be reactedwith an appropriate transition metal compound to form a complex of (I)and the transition metal. For example for early transition metals thismay simply be a halide such as TiCl₄ or ZrCl₄. For late transition metalcomplexes it may also be a halide such as NiBr₂, (COD)NiBr₂ (COD is1,5-cyclooctadiene) or the nickel allyl chloride dimer. In anothermethod of forming the transition metal complex with late transitionmetals the conjugate acid of (I) can be used to protonate a dialkyltransition metal complex such as (TMEDA)Ni(CH₃)₂ (TMEDA isN,N,N′,N′-tetramethylethylenediamine) to form the desired complex. Asnoted above, if the transition metal compound is not at this point anactive polymerization catalyst by itself, appropriate cocatalysts may beadded.

When Z is N, the organometallic compound may be made by the followingscheme, illustrated for Ni. If n is 1, an analogous starting materialmay be used. Complexes of other metals can be made by methods generallydescribed in the immediately preceding paragraph.

If Z is S or PR , and/or Y is O or PR¹², analogous starting materialsand methods may be used to make the ligand and the transition metalcompound.

Preferred monomers herein are hydrocarbon monomers of the formulaH₂C=CHR⁴, or polar olefins of the formula H₂C=CHR⁵CO₂R⁶, andcombinations thereof. A particularly preferred hydrocarbon monomer isethylene (R⁴ is hydrogen). Another preferred hydrocarbon monomer is analpha-olefin (R⁴ is alkyl), particularly when R⁴ is an n-alkylcontaining 1 to 14 carbon atoms, and especially when R⁴ is methyl(propylene). R⁶ may be a metal or onium cation (such as ammonium), inwhich case the polar olefin would be a carboxylate salt. Preferredcations include alkali metal cations and ammonium. For the polarolefins, it is preferred that R⁶ is alkyl, especially alkyl containing 1to 4 carbon atoms, and/or R⁵ is a covalent bond or —(CH₂)_(r)— wherein ris 1 to 19. A particularly preferred combination of monomers is ethylenewith one or more alpha-olefins, polar olefins and/or a cyclopentene,especially ethylene with one or more polar olefins. In all instances thecorresponding copolymers are formed.

When a polar olefin is present as a (co)monomer, it is preferred thatthe transition metal is a late transition metal, particularly Ni, Pd orCu, more preferably Ni. Useful polar olefins include those of thegeneral formula H₂C=CHR¹⁵E, wherein R¹⁵ is alkylene, alkylidene or acovalent bond, especially —(CH₂)_(x)— wherein x is 0 or an integer of 1to 20 and E is a polar group. Useful polar groups E include —CO₂R¹⁴,—CO₂H, —C(O)NR¹⁴ ₂ and —OR¹⁴, and —CO₂R¹⁴ and —OR¹⁴ are more preferred,wherein each R¹⁴ is hydrogen, hydrocarbyl or substituted hydrocarbyl,preferably alkyl or substituted alkyl. For any olefin other than anorbornene, cyclopentene and/or a styrene, it is preferred that it becopolymerized with ethylene. An especially preferred olefin is ethylene(alone). Typically CO and polar comonomers will be used with ahydrocarbon olefin such as ethylene to form a copolymer.

When in the polymerization process and in the metal complex Z is O and Mis Ni, it is preferred that the olefin(s) to be polymerized comprise atleast one polar olefin, except when said complex is further complexedwith a Lewis acid (see above). Also when M is Ni in the transition metalcomplex and Y is NR¹², it is preferred that Z is not O.

In the polymerization process herein, the temperature at which thepolymerization is carried out is about −100° C. to about +200° C.,preferably about −60° C. to about 150° C., more preferably about −20° C.to about 100° C. The pressure of a gaseous olefin such as ethylene atwhich the polymerization is carried out is not critical, atmosphericpressure to about 275 MPa being a suitable range. Liquid olefins may bepresent in virtually any concentration although the polymerization maybe slowed down by high concentrations of polar olefins.

When a polar comonomer and ethylene are present, and a Ni complex(Zwitterionic or not) is used in the polymerization catalyst system, itis preferred that the polymerization process be run at a temperature ofabout 50° C. or more, more preferably 60° C. to about 170° C., and anethylene partial pressure of at least about 700 kPa. More preferably thetemperature range is about 80° C. to about 140° C. and/or a lowerethylene pressure is about 5.0 MPa or more, and/or a preferred upperlimit on ethylene pressure is about 200 MPa, especially preferably about20 MPa. The polymerization process herein may be run in the presence ofvarious liquids, particularly aprotic organic liquids. The catalystsystem, olefinic monomer(s), and/or polymer may be soluble or insolublein these liquids, but obviously these liquids should not prevent thepolymerization from occurring. Suitable liquids include alkanes,cycloalkanes, selected halogenated hydrocarbons, and aromatichydrocarbons. Specific useful solvents include hexane, toluene, benzene,methylene chloride, 1,2,4-trichlorobenzene and p-xylene.

The olefin polymerizations herein may also initially be carried out inthe “solid state” by, for instance, supporting the transition metalcompound on a substrate such as silica or alumina, activating ifnecessary it with one or more cocatalysts and contacting it with theolefin(s). Alternatively, the support may first be contacted (reacted)with cocatalysts (if needed) such as an alkylaluminum compound, and thencontacted with an appropriate transition metal compound. The support mayalso be able to take the place of a Lewis or Bronsted acid, for instancean acidic clay such as montmorillonite, if needed. These “heterogeneous”catalysts may be used to catalyze polymerization in the gas phase or theliquid phase. By gas phase is meant that a gaseous olefin is transportedto contact with the catalyst particle. For the copolymerization of polarolefins using supported catalysts, especially in a liquid medium, apreferred case is when the ligand is covalently attached to the support,which helps prevent leaching of the transition metal complex from thesupport.

In all of the polymerization processes described herein oligomers andpolymers of olefins are made. They may range in molecular weight fromoligomeric POs (polyolefins), to lower molecular weight oils and waxes,to higher molecular weight POs. One preferred product is a PO with adegree of polymerization (DP) of about 10 or more, preferably about 40or more. By “DP” is meant the average number of repeat units in a POmolecule.

Depending on their properties, the POs made by the processes describedherein are useful in many ways. For instance if they are thermoplastics,they may be used as molding resins, for extrusion, films, etc. If theyare elastomeric, they may be used as elastomers. If they containfunctionalized monomers such as acrylate esters, they are useful forother purposes, see for instance previously incorporated U.S. Pat. No.5,880,241.

It is believed that the late transition metal (such as Ni) containingcatalysts used herein often give polymers which have unusual branchingpatterns, see for instance previously incorporated U.S. Pat. No.5,880,241 and Z. Guan, et al., Science, vol. 283 p. 2059-2062 (1999). Onthe other hand, early transition metal (such as Ti and Zr) containingcatalysts usually give polymers with more conventional branching, suchas those made by Ziegler-Natta or metallocene polymerization catalysts.

Depending on the process conditions used and the polymerization catalystsystem chosen, the POs may have varying properties. Some of theproperties that may change are molecular weight and molecular weightdistribution, crystallinity, melting point, and glass transitiontemperature. Except for molecular weight and molecular weightdistribution, branching can affect all the other properties mentioned,and branching may be varied (using the same nickel compound) usingmethods described in previously incorporated U.S. Pat. No. 5,880,241.

It is known that blends of distinct polymers, that vary for instance inthe properties listed above, may have advantageous properties comparedto “single” polymers. For instance it is known that polymers with broador bimodal molecular weight distributions may be melt processed (beshaped) more easily than narrower molecular weight distributionpolymers. Thermoplastics such as crystalline polymers may often betoughened by blending with elastomeric polymers.

Therefore, methods of producing polymers which inherently producepolymer blends are useful especially if a later separate (and expensive)polymer mixing step can be avoided. However in such polymerizations oneshould be aware that two different catalysts may interfere with oneanother, or interact in such a way as to give a single polymer.

In such a process the transition metal containing polymerizationcatalyst disclosed herein can be termed the first active polymerizationcatalyst. A second active polymerization catalyst (and optionally one ormore others) is used in conjunction with the first active polymerizationcatalyst. The second active polymerization catalyst may be another latetransition metal catalyst, for example as described in previouslyincorporated U.S. Pat. Nos. 5,880,241, 6,060,569, 6,174,795 and S. D.Ittel, et al., Chem. Rev., vol. 100, p. 1169-1203 (2000) (and referencescited therein), as well as U.S. Pat. Nos. 5,714,556 and 5,955,555 whichare also incorporated by reference herein as if fully set forth. Otheruseful types of catalysts may also be used for the second activepolymerization catalyst. For instance so-called Ziegler-Natta and/ormetallocene-type catalysts may also be used. These types of catalystsare well known in the polyolefin field, see for instance Angew. Chem.,Int. Ed. Engl., vol. 34, p. 1143-1170 (1995), EP-A-0416815 and U.S. Pat.No. 5,198,401 for information about metallocene-type catalysts, and J.Boor Jr., Ziegler-Natta Catalysts and Polymerizations, Academic Press,New York, 1979 for information about Ziegler-Natta-type catalysts, allof which are hereby included by reference. Many of the usefulpolymerization conditions for all of these types of catalysts and thefirst active polymerization catalysts coincide, so conditions for thepolymerizations with first and second active polymerization catalystsare easily accessible. Oftentimes the “co-catalyst” or “activator” isneeded for metallocene or Ziegler-Natta-type polymerizations. In manyinstances the same compound, such as an alkylaluminum compound, may beused as an “activator” for some or all of these various polymerizationcatalysts.

In one preferred process described herein the first olefin(s) (olefin(s)polymerized by the first active polymerization catalyst) and secondolefin(s) (the monomer(s) polymerized by the second activepolymerization catalyst) are identical. The second olefin may also be asingle olefin or a mixture of olefins to make a copolymer.

In some processes herein the first active polymerization catalystpolymerizes one or more olefins, a monomer that may not be polymerizedby said second active ploymerization catalyst, and/or vice versa. Inthat instance two chemically distinct polymers may be produced. Inanother scenario two monomers would be present, with one polymerizationcatalyst producing a copolymer, and the other polymerization. catalystproducing a homopolymer.

Likewise, conditions for such polymerizations, using catalysts of thesecond active polymerization type, will also be found in the appropriateabove mentioned references.

Two chemically different active polymerization catalysts are used inthis polymerization process. The first active polymerization catalyst isdescribed in detail above. The second active polymerization catalyst mayalso meet the limitations of the first active polymerization catalyst,but must be chemically distinct. For instance, it may utilize adifferent ligand that differs in structure between the first and secondactive polymerization catalysts. In one preferred process, the ligandtype and the metal are the same, but the ligands differ in theirsubstituents.

Included within the definition of two active polymerization catalystsare systems in which a single polymerization catalyst is added togetherwith another ligand, preferably the same type of ligand, which candisplace the original ligand coordinated to the metal of the originalactive polymerization catalyst, to produce in situ two differentpolymerization catalysts.

The molar ratio of the first active polymerization catalyst to thesecond active polymerization catalyst used will depend on the ratio ofpolymer from each catalyst desired, and the relative rate ofpolymerization of each catalyst under the process conditions. Forinstance, if one wanted to prepare a “toughened” thermoplasticpolyethylene that contained 80% crystalline polyethylene and 20% rubberypolyethylene, and the rates of polymerization of the two catalysts wereequal, then one would use a 4:1 molar ratio of the catalyst that gavecrystalline polyethylene to the catalyst that gave rubbery polyethylene.More than two active polymerization catalysts may also be used if thedesired product is to contain more than two different types of polymer.

The polymers made by the first active polymerization catalyst and thesecond active polymerization catalyst may be made in sequence, i.e., apolymerization with one (either first or second) of the catalystsfollowed by a polymerization with the other catalyst, as by using twopolymerization vessels in series. However it is preferred to carry outthe polymerization using the first and second active polymerizationcatalysts in the same vessel(s), i.e., simultaneously. This is possiblebecause in most instances the first and second active polymerizationcatalysts are compatible with each other, and they produce theirdistinctive polymers in the other catalyst's presence. Any of theprocesses applicable to the individual catalysts may be used in thispolymerization process with 2 or more catalysts, i.e., gas phase, liquidphase, continuous, etc.

The polymers produced by this process may vary in molecular weightand/or molecular weight distribution and/or melting point and/or levelof crystallinity, and/or glass transition temperature and/or otherfactors. The polymers produced are useful as molding and extrusionresins and in films as for packaging. They may have advantages such asimproved melt processing, toughness and improved low temperatureproperties.

Catalyst components which include transition metal complexes of (I),with or without other materials such as one or more cocatalysts and/orother polymerization catalysts are also disclosed herein. For example,such a catalyst component could include the Ni complex supported on asupport such as alumina, silica, a polymer, magnesium chloride, sodiumchloride, etc., with or without other components being present. It maysimply be a solution of the complex, or a slurry of the complex in aliquid, with or without a support being present.

Hydrogen or other chain transfer agents such as silanes (for exampletrimethylsilane or triethylsilane) may be used to lower the molecularweight of polyolefin produced in the polymerization process herein. Itis preferred that the amount of hydrogen present be about 0.01 to about50 mole percent of the olefin present, preferably about 1 to about 20mole percent. The relative concentrations of a gaseous olefin such asethylene and hydrogen may be regulated by varying their relative partialpressures.

In the Examples except where noted, all pressures are gauge pressures.In the Examples the following abbreviations are used:

ΔH_(f)—heat of fusion in J/g

Am—amyl

Ar—aryl

BAF—B(3,5-C₆H₃—(CF₃)₂)₄ ⁻

BArF—B(C₆F₅)₄ ⁻

BHT—2,6-di-t-butyl-4-methylphenol

BQ—1,4-benzoquinone

Bu—butyl

Bu₂O—dibutyl ether

CB—chlorobenzene

Cmpd—compound

Cy—cyclohexyl

DMSO—dimethylsulfoxide

DSC—differential scanning calorimetry

E—ethylene

E-10-U—ethyl 10-undecylenate

EG—end-group, refers to the ester group of the acrylate being located inan unsaturated end group of the ethylene copolymer

EGPEA—2-phenoxyethyl acrylate

Eoc—end-of-chain

Equiv—equivalent

Et—ethyl

Et₂O—diethyl ether

GPC—gel permeation chromatography

HA—hexyl acrylate

Hex—hexyl

IC—in-chain, refers to the ester group of the acrylate being bound tothe main-chain of the ethylene copolymer

Incorp—incorporation

i-Pr—i-propyl

LA—Lewis acid

M.W.—molecular weight

MA—methyl acrylate

Me—methyl

MeOH—methanol

MI—melt index

Mn—number average molecular weight

Mp—peak average molecular weight

Mw—weight average molecular weight

Nd—not determined

PDI—polydispersity; Mw/Mn

PE—polyethylene

Ph—phenyl

PMAO—polymethylaluminoxane

Press—pressure

RB—round-bottomed

RI—refractive index

RT or Rt—room temperature

t-Bu—t-butyl

TCB—1,2,4-trichlorobenzene

Temp—temperature

THF—tetrahydrofuran

TO—Number of turnovers per metal center=(moles monomer consumed, asdetermined by the weight of the isolated polymer or oligomers) dividedby (moles catalyst)

TON—turnovers, moles of monomer (olefin) polymerized per mole oftransition metal present

Total Me—total number of methyl groups per 1000 methylene groups asdetermined by 1H or 13C NMR analysis

UV—ultraviolet

All operations related to the ligand/catalyst syntheses were performedin a nitrogen drybox or using a Schlenk line with nitrogen protection.Anhydrous solvents were used. Solvents were distilled from drying agentsunder nitrogen using standard procedures, for instance THF from sodiumbenzophenone ketyl. Ni[II] allyl chloride was prepared according to theliterature (Angew. Chem. Int. Ed. Engl., vol. 5, p. 151-266 (1966)). NMRspectra were recorded using a Bruker 500 MHz spectrometer.

The following transition metal compounds were made:

EXAMPLE 1 Synthesis of A

In a 300 mL RB flask, 5.000 g (0.04545 mole) sodium pyruvate and 8.059 g(0.04545 mole) 2,6-diisopropylaniline were mixed with 150 mL methanol,together with 5 drops of formic acid (96%). The mixture was allowed tostir at RT for 3 d. Some white solid (˜1 g, possibly unreacted sodiumpyruvate) remained and it was filtered off. The resulting solution wasevaporated to dryness. The resulting mixture was dissolved in 80 mLmethanol, followed by addition of 100 mL hexanes and 60 mL THF. A smallamount of white precipitate formed. The mixture was cooled to −40° C.and then was filtered cold, followed by cold hexanes wash. The filtratewas evaporated to dryness. The resulting mixture was stirred withhexanes for 2 h. The white solid was filtered, followed by 3×20 mLhexanes wash and was dried in vacuo. White solid (7.90 g, 65% yield) wasobtained. ¹H NMR (in DMSO-d₆) indicated that it had two isomers (onemajor and one minor) in this solvent: δ6.73-7.13 (m, Ar—H, 3H); 2.98(minor) and 2.71 (major) [m, (CH₃)₂CH—, total 2H], 2.11 (minor) and 1.67(major) [s, N═C—CH₃, total 3H]; 1.05 (pseudo td, (CH₃)₂CH—,³J_(doublet)=6.4 Hz). The structure of A below is a formal structure andmay not completely represent the actual structure.

EXAMPLE 2 Synthesis of 1

In a drybox, A (0.500 g) was mixed with 0.251 g of nickel allyl chloridedimer in 30 mL THF. The color of the solution turned from deep red toyellow brown in a minute. The mixture was stirred for 14 h. THF wasevaporated. The yellow solid was extracted with 30 mL toluene. Themixture was filtered through Celite®, followed by 3×5 mL toluene wash.The solution was concentrated to ca. 5 mL and was added to 50 mL ofpentane. The solid product was filtered, washed with 3×10 mL pentane anddried in vacuo. Yellow solid was obtained (0.424 g, 66% yield). ¹H NMR(in CD₂Cl₂) δ7.16-7.27 (m, Ar—H, 3H); 5.68 (hept, central allyl-H, 1H);3.35 [m, overlapped syn-allyl-H (d, 1H) and (CH₃) ₂CH—, (m, 1H), total2H]; 2.92 (m, (CH₃)₂CH—, 1H); 2.35 (d, ³J=13.2 Hz,anti-terminal-allyl-H, 1H); 2.01 (d, ³J=6.0 Hz, syn-terminal-allyl-H,1H); 1.91 (s, N═C—CH₃, total 3H]; 1.87 (d, ³J=13.2 Hz,anti-terminal-allyl-H, 1H); 1.33 (d, ³J=6.4Hz, (CH₃)₂CH—, 3H); 1.27 (d,³J=6.5Hz, (CH₃)₂CH—, 3H); 1.19 (d, ³J=6.4Hz, (CH₃)₂CH—, 3H); 1.09 (d,³J=6.5Hz, (CH₃)₂CH—, 3H). A single crystal of 1 was grown by slowevaporation of its methylene chloride/heptane solution. X-ray crystalstructure of 1 was consistent with the proposed structure. The bonddistance of the carbon-oxygen bond (the oxygen atom connected with Ni,C₁-O₁) was 1.277 (4) Å, indicating that it is a single bond. The bonddistance of the carbonyl carbon-oxygen bond (C₁-O₂) was 1.229(4) Å,indicating it was a double bond.

EXAMPLE 3 Synthesis of 2

In a drybox, A (1.500 g) was mixed with 0.753 g of nickel allyl chloridedimer in 50 mL THF. The mixture was stirred at RT for 5 h. THF wasevaporated. The residue was extracted with 70 mL toluene. The mixturewas filtered through Celite®, followed by 3×10 mL toluene wash. To thissolution under stirring was added 2.9082 g B(C₆F₅)₃. The solution wasallowed to stir for 2 h. The cloudy solution was filtered throughCelite®, followed by 3×10 mL toluene wash. The filtrate was concentratedto dryness. The residue was dissolved in ca. 20 mL methylene chloride,followed by addition of ca. 150 mL pentane. The orange solid wasfiltered, washed with 3×10 mL pentane and dried in vacuo. Orange solidwas obtained (1.450 g, 30% yield). ¹H NMR (in CD₂Cl₂) δ7.22-7.35 (m,Ar—H, 3H); 5.72 (hept, central allyl-H, 1H); 3.42 (d,syn-terminal-allyl-H, J=8.5 Hz, 1H); 3.22, 2.81 (m, CH₃)₂CH—, 1H each];2.44 (d, ³J=17.2 Hz, anti-terminal-allyl-H, 1H); 2.35 (d, ³J=8.2 Hz,syn-terminal-allyl-H, 1H); 2.09 (s, N═C—CH₃, 3H); 2.05 (d, ³J=16.8 Hz,anti-terminal-allyl-H, 1H); 1.36 (d, ³J=8.4 Hz, (CH₃)₂CH—, 3H); 1.30 (d,³J=8.4 Hz, (CH₃)₂CH—, 3H); 1.25 (d, ³J=8.4 Hz, (CH₃)₂CH—, 3H); 1.15 (d,³J=8.5 Hz, (CH₃)₂CH—, 3H). ¹⁹F NMR in CD₂Cl₂: δ-135.74 (d, J=21.6 Hz,o-F, 2F); -160.60 (t, p-F, 1F); -166.40 (t, m-F, 2F). An orange-redsingle crystal of complex 2 was grown by slow evaporation of a methylenechloride/heptane solution. X-ray crystal structure was consistent withthe proposed Zwitterion complex. The bond distance of the carbon-oxygenbond (the oxygen atom connected with Ni, C₁-O₁) was 1.241(3) Å,indicating that it had become a double bond. The bond distance of thecarbon-oxygen bond (the oxygen atom connected with boron C₁-O₂) was1.278(3) Å, indicating it had become a single bond. Anal. Calcd forC₃₆H₂₅BF₁₅NNiO₂: C, 50.39; H 2.94; N 1.63. Found: C, 50.08; H, 2.86; N,1.60.

EXAMPLE 4 Synthesis of 3

In a drybox, to a TiCl₄ THF solution (0.3522 g in 20 mL THF) was added0.5000 g A in portions at RT. The resulting mixture was allowed to stirovernight. The mixture was then filtered through Celite®, followed by2×5 mL THF wash. The filtrate was evaporated to dryness. The resultingsolid was dried in vacuo. Black crystalline solid (0.9026 g) wasobtained.

EXAMPLE 5 Synthesis of 4

In a drybox, to a TiCl₄ THF solution (0.1761 g in 20 mL THF) was added0.5000 g A in portions at RT. The resulting mixture was allowed to stirovernight. The mixture was then filtered through Celite®, followed by2×5 mL THF wash. The filtrate was evaporated to dryness. The resultingsolid was dried in vacuo. Dark green solid (0.6441 g, 92%) was obtained.¹H NMR in THF-d₈: δ7.03-7.17 (m, Ar—H, 6H); 2.66 (hept, CH₃)₂CH—, 4H),1.90 (s, N═C—CH₃, 6H); 1.13 (d, ³J=7.0 Hz, (CH₃)₂CH—, 12H); 1.11 (d,³J=6.8 Hz, (CH₃)₂CH—, 12H)

EXAMPLE 6 Synthesis of 5

In a drybox, to a ZrCl₄ THF solution (0.4326 g in 20 mL THF) was added0.5000 g A in portions at RT. The resulting mixture was allowed to stirovernight. The mixture was then filtered through Celite®, followed by2×5 mL THF wash. The filtrate was evaporated to dryness. The resultingsolid was dried in vacuo. Tan solid (0.9319 g) was obtained.

EXAMPLE 7 Synthesis of 6

In a drybox, to a ZrCl₄ THF solution (0.2163 g in 20 mL THF) was added0.5000 g A in portions at RT. The resulting mixture was allowed to stirovernight. The mixture was then filtered through Celite®, followed by2×5 mL THF wash. The filtrate was evaporated to dryness. The resultingsolid was dried in vacuo. Pale yellow solid (0.6136 g) was obtained.

EXAMPLEs 8-19 Ethylene Polymerization Using 1 and 2

In a drybox, a glass insert was loaded with the isolated Ni compounds.Solvent and optionally comonomers were added to the glass insert. ALewis acid cocatalyst [typically BPh₃ or B(C₆F₅)₃] was often added tothe solution. The insert was then capped and sealed. Outside of thedrybox, the tube was placed under ethylene and was shaken mechanicallyat desired temperature listed in Table 1 for about 18 h. The resultedreaction mixture was blended with methanol, filtered, repeatedly washedwith methanol and dried in vacuo.

Ethylene Polymerization by 3-6, in the Presence of PMAO

In a drybox, a glass insert was loaded with 0.02 mmol of the isolated Zror Ti compound and 9 mL of 1,2,4-trichloro-benzene. It was then cooledto −30° C. PMAO [1 mL, 12.9 wt % (in Al) toluene solution] was added tothe frozen solution. It was put in the −30° C. freezer. The insert wasthen capped and sealed. Outside of the drybox, the cold tube was placedunder ethylene and was shaken mechanically at desired temperature listedin Table 1, condition IV, for about 18 h. Methanol (about 15 mL) and 2mL conc. hydrochloric acid was added to the mixture. The polymer wasisolated, washed with methanol several times and dried in vacuo.

Detailed conditions for the various polymerizations are given in Table2.

TABLE 2 Polymerization Conditions Condi- tion I 0.02 mmol catalyst, 10mL TCB, RT, 18 h, 6.9 MPa ethylene II 0.02 mmol catalyst, 6 mL TCB, 4 mLHA, 100° C., 18 h, 6.9 MPa ethylene, 40 eq B(C₆F₅)₃ III 0.02 mmolcatalyst, 6 mL TCB, 4 mL HA, EGPEA or E-10-U, 120° C., 18 h, 6.9 MPaethylene, 40 eq B(C₆F₅)₃ IV 0.02 mmol catalyst, 9 mL TCB, 1 mL PMAO-IP[12.9 wt % (in Al) in toluene), RT, 18 h, 6.9 MPa ethylene

Polymer Characterization

The results of the ethylene polymerization and copolymerizationcatalyzed by 1-6 under different reaction conditions (See Table 2) arereported in Tables 3-6. The polymers were characterized by NMR, GPC andDSC analysis. A description of the methods used to analyze the amountand type of branching in polyethylene is given in previouslyincorporated U.S. Pat. No. 5,880,241. GPC's were run in trichlorobenzeneat 135° C. and calibrated against polyethylene using universalcalibration based on polystyrene narrow fraction standards. DSC wasrecorded between −100° C. to 150° C. at a rate of 10° C./minute. Datareported here are all based on second heat. Melting points were taken asthe peak of the melting endotherm. ¹H NMR of the polymer samples was runin tetrachloroethane-d₂ at 120° C. using a 500 MHz Bruker spectrometer.

TABLE 3 Ethylene Polymerization Under Condition I Cocatalyst/ Yield #Me/m.p., (° C.) Example Catalyst amt. (g) 1000CH₂ [ΔH_(f)] Mw/PDI TON 8 1B(C₆F₅)₃/10eq 7.700 40 127 [106] 248,950/2.2  13,724  second modal MP =2,826  9 1 BPh₃/10eq 0.570 10 129 [165] 225,378/2.8 1,016 10 1 none 0 // / / 11 2 none 3.000  8 130 [156] 232,371/4.0* 5347 *It has a smalltail at MP = 674

TABLE 4 Ethylene/HA Copolymerization Under Condition II Mole % m.p.,Exam- Cata- Yield #Me/ Comon- (° C.) Mw/ TON ple lyst (g) 1000CH₂ omer[ΔH_(f)] PDI E/HA 12 2 2.067* 24 3.9 106 7,664/ 3,009/ [120] 2.3 121 *Inaddition to 2.067 g copolymer, HA homopolymer (0.567 g) was alsoproduced.

TABLE 5 Ethylene Copolymerization under Condition III Comonomer Yield#Me/ m.p. TON Ex. Catalyst (Mole %) (g) 1000CH₂ (° C.) [ΔH_(f)] Mw/PDIE/Comonomer 13 2 HA (4.4) 2.543* 29  97 [86.3] 6,688/2.7 3,587/170 14 2EGPEA 3.182** 22 100 [88.8] 9,821/3.3 4,989/100 (2.0) 15 2 E-10-U (2.3)18.252 24  93 [109] 17,455/6.2  27,689/640  115 *Contained 2.543 gcopolymer and 0.772 g homopolymer of HA **Contained 3.182 g copolymerand 1.963 g homopolymer of EGPEA

TABLE 6 Ethylene Polymerization under Condition IV Yield m.p., (° C.)Example Catalyst (g) [ΔH_(f)] TON 16 3 12.060 134 [132] 21,496 17 411.607 134 [143] 20,688 18 5 7.850 131 [133] 13,992 19 6 7.317 132 [144]13,042

EXAMPLES 20-27

A 600 mL Parr® reactor was cleaned, heated up under vacuum, and thenallowed to cool down under nitrogen. In a drybox, 8.1 mg (0.0094 mmole)of 2 and optionally Lewis acid were dissolved in 90 mL toluene and 60 mLE-10-U in a 300 mL RB flask. The flask was sealed using a rubber septum.Outside the drybox, an oil bath was prepared (see Table 7 fortemperature). The RB flask was removed from the drybox. The solution wastransferred via cannula into the autoclave under positive nitrogenpressure. The autoclave was sealed and pressurized to 690 kPa nitrogen.Nitrogen was then vented. The pressuring/venting was repeated two moretimes. At about 35 kPa nitrogen, the autoclave was stirred at about 600RPM. Ethylene pressure (˜4.8 MPa) was applied. The autoclave was quicklyplaced in the preheated bath. The pressure of the autoclave was adjustedto about 5.9 MPa and the temperature of the bath was adjusted to makethe reaction mixture's temperature stabilize around the temperaturelisted in Table 7. It was stirred at this temperature and pressure for atime period indicated in Table 7. The heating source was removed andethylene was vented. The autoclave was back-filled with 0.7 MPa nitrogenand nitrogen was vented after brief stirring. This was repeated two moretimes. The room temperature mixture was poured into 50 mL methanol,filtered, and washed with methanol. The resulting polymer was blendedwith methanol, filtered, and washed with methanol. The blending/washingprocedure was repeated two more times. The white polymer was dried invacuo overnight. Results are given in Table 7.

TABLE 7 Ethylene/E-10-U Copolymerizations Temp. Time Equiv. Yield E-10-U#Me/ m.p. (° C.) Ex. (° C.) (hr) Lewis Acid (g) (Mole %) 1000CH₂(ΔH_(f)) Mw/PDI 20 80 2 none 12.08 1.4 13 114 (142.1) 27,643/3.2 21 80 280 BPh₃ 19.18 1.2 13 115 (145.8) 29,669/2.7 22 80 4 80 BPh₃ 36.63 1.4 13113 (139.2) 28,028/2.7 23 70 6 80 BPh₃ 41.71 0.8 9 119 (149.3)37,279/2.4 24 60 6 80 BPh₃ 27.17 0.7 8 120 (142.9) 49,158/2.3 25 80 2 10BPh₃ 16.83 1.1 11 114.8 (153.8)   27,497/3.3 26 80 2 10 B(C₆F₅)₃ 36.811.0 14 115 (142.6) 27,255/3.4 27 80 2 80 B(C₆F₅)₃ 42.40 1.1 13 115(144.2) 26,940/2.8

EXAMPLE 28 EHA Copolymerization Using a 600 cc Parr® Reactor

A 600 mL Parr® reactor was cleaned, heated up under vacuum, and thenallowed to cool down under nitrogen. In a drybox, 16.1 mg of 2, 3.072 g(6 mmole, 320 eq to Ni catalyst) tris(pentafluorophenyl)boron, and 1.029g (1.5 mmole, 80 eq to Ni catalyst) lithiumtetrakis(pentafluorophenyl)borate were dissolved in 120 mL1,2,4-trichlorobenzene and 30 mL (HA) in a 300 mL RB flask. It wassealed using a rubber septum. Outside the drybox, a 100° C. oil bath wasprepared. The RB flask was removed from the drybox. The solution wastransferred via cannula into the autoclave under positive nitrogenpressure. The autoclave was sealed and pressurized to 690 kPa nitrogen.Nitrogen was then vented. The pressuring/venting s repeated two moretimes. At about 35 kPa nitrogen, the autoclave was stirred at about 600RPM. Ethylene pressure ˜4.1 MPa) was applied. The autoclave was quicklyplaced in the preheated 100° C. bath. The pressure of the autoclave wasadjusted to about 6.3 MPa and the temperature of the bath was adjustedto make the reaction temperature about 80° C. It was stirred at thistemperature and pressure for 6 h. The heating source was removed andethylene was vented. The autoclave was back-filled with 690 kPa nitrogenand nitrogen was vented after brief stirring. This was repeated two moretimes. The room temperature mixture was poured into 500 mL methanol,filtered, and washed with methanol. The resulting polymer was blendedwith methanol, filtered, and washed with methanol. It was dried in vacuoovernight. White polymer solid (5.321 g) was obtained. GPC (135° C.,TCB) : Mw=14,006; Mn=6,294; PDI=2.2. The polymer has a melting point of113° C. (126.2 J/g) based on DSC. ¹³CNMR: 1.1 mole % HA incorporation.Total Me: 17.0 (9.1 Me; 1.7 Et; 1.5 Pr; 0.3 Bu; 4.9 Bu⁺; 2.8 Am⁺ and 0.6Hex⁺).

EXAMPLES 29-33

TABLE 8 Ethylene/Polar Monomer Copolymerization Using 0.02 mmole 2, withor without B(C₆F₅)₃, with a Total Volume of 10 mL of TCB and PolarMonomer, under 80° C. at 3.4 MPa of Ethylene Polar Polar Monomer YieldEx Catalyst B(C₆F₅)₃ Monomer Volume (mL) (g) 29 2 40 eq

2 3.361 30 2  0 eq

3 3.566 31 2 40 eq CH₂═CH(CH₂)₂C(O)CH₃ 3 0.116 32 2 40 eq

3 0.338 33 2 40 eq CH₂═CH(CH₂)₇C(CH₂O)₃CCH₃ 3 11.202 

EXAMPLE 34

An ethylene/CO copolymerization using 0.02 mmole 2, 40 eq B(C₆F₅)₃, 10mL TCB, at 100° C. under 2.8 MPa E/CO (9:1 ratio) was carried out for 16h. The polymer yield was 0.048 g.

EXAMPLES 35-40 General Details of Ligand and Catalyst Synthesis forCmpds G-1 through G-4

Nickel compounds G-1 and G-2 were synthesized according to eqs 1-4 andcompounds G-3 and G-4 were synthesized according to eqs 1, 4 and 5.

Precursors: Pyruvic acid chloride [Me—C(O)—C(O)—Cl] and phenylglyoxylicacid chloride [Ph—C(O)—C(O)—Cl], which were used for the ligandsyntheses, were prepared by literature procedures: H. C. J. Ottenhedn,et al., Synthesis, 1975, 163-164. The acid chlorides were redistilled 3times to achieve desirable purity.

Amido Compounds: The syntheses and characterization of amido derivativesof pyruvic acid chloride and phenylglyoxylic acid chloride are given inthe examples below.

Imine Compounds: The keto-amido compounds were converted into iminesaccording to standard literature methods: tom Dieck, H.; Svoboda, M.;Grieser, T. Z. Naturforsch, vol. 36b, p. 832 (1981). Typically, a smallexcess of aniline was added to the keto-amido compound in methanoltogether with a catalytic amount of formic acid. The reaction mixturewas stirred for several days and the precipitate was collected on afrit, washed with methanol, and dried in vacuo to give the correspondingimino-amido compound.

Sodium Amides: Deprotonations of the amido compounds were carried out ina nitrogen-filled drybox. In general, the amido compound (several grams)was placed in a round bottom flask and dissolved in ˜40 mL of THF.Excess NaH was added and the reaction mixture was stirred for severaldays. The reaction mixture was filtered through a frit with Celite® andthe solvent was removed in vacuo to yield the sodium salt of the ligand.

Nickel Complexes: The nickel complexes G-1 through G-4 were synthesizedby stirring a THF solution of the sodium salt of the correspondingligand (1 equiv) and the appropriately substituted [(allyl)Ni(halide)]₂precursor (0.5 equiv) in a nitrogen-filled drybox overnight. Thesolution was then filtered through a frit with dry Celite® and thesolvent was removed in vacuo. The product was redissolved in Et₂O ortoluene and the resulting solution was filtered. The solvent was removedin vacuo. The product was washed with pentane and then dried in vacuo.

EXAMPLE 35 2,6-Di-iso-propylanilide of Pyruvic Acid

Pyruvic acid chloride (4.0 g, 0.038 mole) was dissolved in 200 mL ofethyl ether. A mixture of 7.3 g (0.041 mole) of 2,6-di-iso-propylanilineand 4.2 9 (0.042 mole) of triethylamine in 100 mL of ethyl ether wasthen added dropwise to the solution of pyruvic acid chloride. Thereaction mixture was stirred overnight and then the formed solids wereremoved by filtration. Removal of the solvent in vacuo yielded theproduct, which was further purified by recrystallization from pentane.The yield of the 2,6-di-iso-propylanilide of pyruvic acid was 2.9 g(31%) with m.p. 116.70° C. ¹³C NMR (CD₂Cl₂) δ160.61 (s, O═C—N), 198.09(s, Me—C═O). GC/MS m/z 247; calcd: 247. Anal. Calcd. for C₁₅H₂₁NO₂: C,72.77; H, 8.49; N, 5.66. Found: C, 72.54; H, 8.01; N, 5.97.

2,4,6-Trimethylanilide of Pyruvic Acid

Pyruvic acid chloride (4.0 g, 0.038 mole) was dissolved in 200 mL ofethyl ether. A mixture of 5.6 g (0.041 mole) of 2,4,6-trimethylanilineand 3.8 g (0.038 mole) of triethylamine in 100 mL of ethyl ether wasadded dropwise to the solution of pyruvic acid chloride. The reactionmixture was stirred overnight and then the formed solids were removed byfiltration. Removal of the solvent in vacuo yielded the product, whichwas further purified by recrystallization from pentane. The yield of the2,4,6-trimethylanilide of pyruvic acid was 3.9 g (51%) with m.p. 53.44°C. ¹³C NMR (CD₂Cl₂) δ159.28 (s, O═C—N), 198.07 (s, Me—C═O). GC/MS: m/z205; calcd 205. Anal. Calcd. for C₁₂H₁₅NO₂: C, 70.16; H, 7.31; N, 6.86.Found: C, 71.03; H, 7.64; N, 7.04.

EXAMPLE 37

t-Butylamide of Pyruvic Acid

Pyruvic acid chloride (9.5 g, 0.089 mole) was dissolved in 200 mL ofethyl ether. A mixture of 7.18 g (0.098 mole) of tert-butylamine and 9.9g (0.098 mole) of triethylamine in 100 mL of ethyl ether was addeddropwise to the solution of pyruvic acid chloride. The reaction mixturewas stirred overnight and then the formed solids were removed viafiltration. Removal of the solvent in vacuo yielded the product, whichwas purified by distillation at 51° C./50 mm. The yield of thetert-butylamide of pyruvic acid was 3.7 g (29%). ¹³C NMR (CD₂Cl₂)δ157.99 (s, O═C—N), 196.52 (s, Me—C═O). GC/MS: m/z 143; calcd 143. Anal.Calcd. for C₇H₁₃NO₂: C, 58.66; H, 9.08; N, 9.78. Found: C, 58.46; H,9.15; N, 9.43.

EXAMPLE 38

2,6-Di-i-propylanilide of Benzoylformic Acid

Benzoylformic chloride (5.0 g, 0.03 mole) was dissolved in 100 mL ofethyl ether. A mixture of 5.8 g (0.033 mole) of 2,6-di-i-propylanilineand 3.2 g (0.032 mole) of triethylamine in 100 mL of ethyl ether wasadded dropwise to the solution of benzoylformic acid chloride. Thereaction mixture was stirred overnight and then the formed solids wereremoved by filtration. Removal of the solvent in vacuo yielded theproduct, which was further purified by recrystallization from pentane.The yield of the 2,6-di-i-propylanilide of benzoylformic acid was 5.4 g(59%) with m.p. 188.53° C. ¹³C NMR (CD₂Cl₂) δ160.47 (s, O═C—N), 186.98(s, Ph—C═O). GC/MS: m/z 309; calcd 309. Anal. Calcd. for C₂₀H₂₃NO₂: C,77.57; H, 7.43; N, 4.52. Found: C, 77.35; H, 7.34; N, 4.53.

EXAMPLE 39

2,4,6-Trimethylanilide of Benzoylformic Acid

Benzoylformic chloride (5.2 g, 0.031 mole) was dissolved in 100 mL ofethyl ether. A mixture of 4.6 g (0.034 mole) of 2,4,6-trimethylanilineand 3.43 g (0.035 mole) of triethylamine in 100 mL of ethyl ether wasadded dropwise to the solution of benzoylformic acid chloride. Thereaction mixture was stirred overnight and the formed solids wereremoved by filtration. Removal of the solvent in vacuo yielded theproduct, which was further purified by recrystallization from pentane.The yield of the 2,4,6-trimethylanilide of benzoylformic acid was 5.7 g(69%) with m.p. 208.48 ° C. ¹³C NMR (CD₂Cl₂) δ161.33 (s, O═C—N), 188.94(s, Ph—C═O). GC/MS: m/z 267; calcd 267. Anal. Calcd. for C₁₇H₁₇NO₂: C,76.31; H, 6.36; N, 5.24. Found: C, 76.05; H, 6.13; N, 5.17.

EXAMPLE 40

t-Butylamide of Benzoylformic Acid

Benzoylformic chloride (5.05 g, 0.0299 mole) was dissolved in 100 mL ofethyl ether. A mixture of 3.29 g (0.045 mole) of tert-butylamine and3.33 g (0.033 mole) of triethylamine in 100 mL of ethyl ether was addeddropwise to the solution of benzoylformic acid chloride. The reactionmixture was stirred overnight and the formed solids were then removed byfiltration. Removal of the solvent in vacuo yielded the product, whichwas then purified by recrystallization from pentane. The yield of thetert-butylamide of benzoylformic acid was 3.12 g (51%) with m.p. 78.96°C. ³C NMR (CD₂Cl₂) δ160.37 (s, O═C—N) , 187.69 (s, Ph—C═O). GC/MS: m/z205; calcd 205. Anal. Calcd. for C₁₂H₁₅NO₂: C, 70.15; H, 7.31; N, 6.82.Found: C, 69.92; H, 7.08; N, 6.79. The structure of this compound wasconfirmed by a single-crystal X-ray diffraction study.

EXAMPLES 41-48 General Details of the Polymerizations with Ni Cmpds G-1Through G-4

The polymerizations were carried out according to General PolymerizationProcedure A below. Varying amounts of acrylate homopolymer are presentin some of the isolated polymers. In Table 9, the yield of the polymeris reported in grams and includes the yield of the dominantethylene/acrylate copolymer as well as the yield of any acrylatehomopolymer that was formed. Molecular weights were determined by GPC,unless indicated otherwise. Mole percent acrylate incorporation andtotal Me were determined by ¹H NMR spectroscopy, unless indicatedotherwise. Mole percent acrylate incorporation is typicallypredominantly IC, unless indicated otherwise. The LiBArF used had 2.5equiv of Et₂O coordinated.

General Procedure A for Ethylene Polymerizations and Copolymerizations

In a nitrogen-filled drybox, a 40 mL glass insert was loaded with thenickel compound and, optionally, a Lewis acid (e.g., BPh₃ or B(C₆F₅)₃)and borate (e.g., NaBAF or LiBArF) and any other specified cocatalysts.Next, the solvent was added to the glass insert followed by the additionof any co-solvents and then comonomers. The insert was greased andcapped. The glass insert was then loaded in a pressure tube inside thedrybox. The pressure tube was then sealed, brought outside of thedrybox, connected to the pressure reactor, placed under the desiredethylene pressure and shaken mechanically. After the stated reactiontime, the ethylene pressure was released and the glass insert wasremoved from the pressure tube. The polymer was precipitated by theaddition of MeOH (˜20 mL). The polymer was then collected on a frit andrinsed with MeOH and, optionally, acetone. The polymer was transferredto a pre-weighed vial and dried under vacuum overnight. The polymeryield and characterization were then obtained.

General Information Regarding Molecular Weight Analysis

GPC molecular weights are reported versus polystyrene standards. Unlessnoted otherwise, GPC's were run with RI detection at a flow rate of 1mL/min at 135° C. with a run time of 30 min. Two columns were used:AT-806MS and WA/P/N 34200. A Waters RI detector was used and the solventwas TCB with 5 grams of BHT per gallon. Dual UV/RI detection GPC was runin THF at rt using a Waters 2690 separation module with a Waters 2410 RIdetector and a Waters 2487 dual absorbance detector. Two Shodex columns,KF-806M, were used along with one guard column, KF-G. In addition toGPC, molecular weight information was at times determined by ¹H NMRspectroscopy (olefin end group analysis) and by melt index measurements(g/10 min at 190° C.).

TABLE 9 Ethylene Homopolymerizations and Ethylene/AcrylateCopolymerizations with Cmpds G-1 through G-4 (10 mL Total Volume ofp-Xylene and Acrylate, 18 h) B(C₆F₅)₃ Acrylate Cmpd Acrylate equiv PressTemp Yield Incorp. Total Ex. (mmol) mL (Borate equiv) MPa ° C. g mol %M.W. Me 41 G-1 None 40 1.0 60 7.02  — M_(n)(¹H) =12,490 32.4 (0.005)(None) 42 G-2 None 40 1.0 60 5.34  — M_(n)(¹H) = 6,810 34.0 (0.005)(None) 43 G-1 EGPEA 200  6.9 120 0.668 3.42^(a) M_(p) = 4,608; 23.8(0.002) 1 (NaBAF 2.64 IC M_(w) = 5,421; 100)  0.78 EG M_(n) = 2,723; PDI= 1.99 44 G-2 EGPEA 200  6.9 120 0.219 5.75^(a) M_(p) = 4,789 26.4(0.002) 1 (NaBAF 3.73 IC M_(w) = 5,608; 100)  2.02 EG M_(n) = 2,872; PDI= 1.95 45 G-1 EGPEA 20 6.9 120 1.66 2.4 M_(p) = 4,676; 37.8 (0.02)  1(NaBAF M_(w) = 5,912; 10) M_(n) = 2,865; PDI= 2.06 46 G-2 EGPEA 20 6.9120 3.73 1.6 M_(p) = 4,517; 44.9 (0.02)  1 (NaBAF M_(w) = 5,222; 10)M_(n) = 1,985; PDI = 2.63 47 G-3 HA 80 6.9 120 0.009 1.7 M_(n)(¹H) =1,229 75.3 (0.005) 1 (LiBArF 40) 48 G-4 HA 80 6.9 120 0.021 0.9^(a)M_(n)(¹H) = 5,034 19.8 (0.005) 1 (LiBArF IC & EG 40) ^(a)The percentacrylate incorporation is an approximation due to the large amount ofhomopolymer present.

EXAMPLE 49 Values of LAIC for a Variety of Catalysts

The following values of LAIC were obtained by constructing models of thecomplexes with Dreiding Models and measuring the respective angles anddistances. The structures shown are to indicate the connectivity of themodel, but the measurements were taken on the actual models.

θ = 130°, λ = 7 Å θ = 105°, λ = 5 Å θ = 95°, λ = 4.5 Å

θ = 80°, λ = 3 Å θ = 75°, λ = 3 Å θ = 75°, λ = 3 Å

θ = 70°, λ = 3 Å θ = 65°, λ = 3 Å

What is claimed is:
 1. A process for the polymerization of olefins,comprising the step of contacting, under olefin polymerizing conditions,a monomer component comprising one or more of an olefin of the formulaH₂C═CHR⁴, a norbornene, a styrene, a cyclopentene or a polar olefin,with a transition metal complex of a ligand of the formula

wherein: Y is oxo, NR¹² or PR¹² Z is O, NR¹³, S or PR¹³; each of R¹, R²and R³ is independently hydrogen, hydrocarbyl, substituted hydrocarbylor a functional group; n is 0 or 1; R⁴ is hydrogen, alkyl or substitutedalkyl; R⁵ is a covalent bond, alkylene or substituted alkylene; R⁶ ishydrogen, a metal cation, hydrocarbyl or substituted hydrocarbyl; eachR¹² is independently hydrogen, hydrocarbyl, substituted hydrocarbyl or afunctional group; each R¹³ is independently hydrogen, hydrocarbyl,substituted hydrocarbyl or a functional group; and provided that: anytwo of R¹, R² and R³ geminal or vicinal to one another taken togethermay optionally form a ring, and when Z is O and Y is NR¹², n is
 1. 2.The process of claim 1, wherein the transition metal is a Group 3-11transition metal.
 3. The process of claim 2, wherein the transitionmetal is selected from the group consisting of Ni, Zr, Ti, Fe, Co andCu.
 4. The process of claim 1, wherein Z is O or NR¹³ and n is
 0. 5. Theprocess of claim 1, wherein: Y is oxo, Z is NR¹³, R¹ is hydrogen orhydrocarbyl, n is 0, and R¹³ is hydrocarbyl or substituted hydrocarbylhaving an E_(s) of less than −1.0 or aryl or substituted aryl in whichat least one bond vicinal to the free bond of the aromatic group issubstituted; or Y is NR¹² and Z is NR¹³, n is 0, R¹ is hydrogen orhydrocarbyl, R¹² and R¹³ are each independently hydrocarbyl orsubstituted hydrocarbyl, one or both of which has an E_(s) of less than−1.0, or aryl or substituted aryl in which at least one bond vicinal tothe free bond of the aromatic group is substituted.
 6. The process ofclaim 1, wherein the transition metal complex has the formula(L¹)_(x)(L²)_(y)(L³)_(z)M (VIII), wherein L³ is (I); z is 1 or 2; M is atransition metal of oxidation state q; y is an integer of 1 to 3;x=(q−z); each L¹ is independently a monodentate, monoanionic ligand,wherein at least one L¹ group is a ligand that adds to an olefin; and L²is a monodentate neutral ligand which is displaced by an olefin, or anempty coordination site; or L¹ and L² taken together are a monoanionic,bidentate ligand into which an olefin molecule inserts between theligand and M.
 7. The process of claim 1, wherein the transition metalcomplex has the formula

wherein M is the transition metal; each L¹ is independently amonodentate, monoanionic ligand, wherein at least one L¹ group is aligand that adds to an olefin; and L² is a monodentate neutral ligandwhich is displaced by an olefin, or an empty coordination site; or L¹and L² taken together are a monoanionic, bidentate ligand into which anolefin molecule inserts between the ligand and M.
 8. The process ofclaim 1, wherein a cocatalyst is present.
 9. The process of claim 1,wherein the monomer component comprises ethylene.